Polyolefin

ABSTRACT

The present invention relates to polyolefin. More specifically, the present invention relates to polyolefin having excellent dart drop impact strength, and exhibiting improved transparency, and such polyolefin has a density of 0.915 g/cm3 to 0.930 g/cm3 measured according to ASTM D1505; and satisfies the following requirements (provided that S1+S2+S3=1), when measuring the relative content of peak area according to melting temperature (Tm) using SSA (Successive Self-nucleation and Annealing) analysis: the content(S1) of peak area at Tm less than 100° C. is 0.33 to 0.35; the content(S2) of peak area at Tm of 100° C. or more and 120° C. or less is 0.52 to 0.56; and the content(S3) of peak area at Tm greater than 120° C. is 0.10 to 0.14.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a national phase entry under 35 U.S.C. § 371 ofInternational Application No. PCT/KR2019/018225 filed Dec. 20, 2019,which claims priority from Korean Patent Application No. 10-201 8-0167766 filed Dec. 21, 2018, all of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION (a) Field of the Invention

The present invention relates to polyolefin. More specifically, thepresent invention relates to polyolefin that has improved mechanicalproperties such as excellent dart drop impact strength, and may exhibitimproved transparency when preparing a film.

(b) Description of the Related Art

Linear low density polyethylene(LLDPE) is prepared by copolymerizationof ethylene and alpha olefin at low pressure using a polymerizationcatalyst, and it has narrow molecular weight distribution and shortchain branches of a certain length, and does not have long chainbranches. A linear low density polyethylene film has high elongation andbreaking strength, and excellent tear strength and dart drop impactstrength, as well as general properties of polyethylene, and thus, theuse is increasing in stretch films, overlap films, and the like, forwhich the existing low density polyethylene or high density polyethylenecannot be applied.

However, linear low density polyethylene has poor blown filmprocessability and low transparency, compared to excellent mechanicalproperties. A blown film is a film prepared by blowing air in moltenplastic to inflate, and it is also referred to as an inflation film.

Meanwhile, as the density of linear low density polyethylene is lower,dart drop impact strength increases. However, if a lot of comonomers areused to prepare low density polyethylene, fouling may be frequentlygenerated in a slurry polymerization process.

Meanwhile, processability may be improved by introducing LCB(long chainbranch) in linear low density polyethylene, but transparency and dartdrop impact strength are deteriorated as LCB increases.

Thus, there is a demand for the development of polyethylene that has lowdensity and can realize excellent mechanical properties such as dartdrop impact strength as well as transparency.

PRIOR ART

(Patent Document 1) Korean Laid-Open Patent Publication No. 2010-0102854

SUMMARY OF THE INVENTION

In order to solve the problem of the prior art, it is an object of thepresent invention to provide polyolefin that has low density andimproved mechanical properties such as excellent dart drop impactstrength, and may exhibit improved transparency when preparing a film.

In order to achieve the object, the present invention providespolyolefin having density of 0.915 g/cm³ to 0.930 g/cm³; and

satisfying the following requirements 1) to 3)(provided that S₁+S₂+S₃=1), when measuring the relative content of peak area according to meltingtemperature (Tm) using SSA (Successive Self-nucleation and Annealing)analysis:

1) the content(S₁) of peak area at Tm less than 100° C. is 0.33 to 0.35;

2) the content(S₂) of peak area at Tm of 100° C. or more and 120° C. orless is 0.52 to 0.56; and

3) the content(S₃) of peak area at Tm greater than 120° C. is 0.10 to0.14.

According to the present invention, during the polymerization ofpolyolefin using a metallocene catalyst, polyolefin having optimumlamellar distribution can be provided by appropriately controlling therelative content of crystal peaks according to melting temperature.

Thereby, polyolefin having excellent transparency and high dart dropimpact strength can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the temperature profile of SSA analysisaccording to one embodiment of the invention.

FIG. 2 is a graph showing the relation between the density and dart dropimpact strength of polyolefin according to Examples and ComparativeExamples.

FIG. 3 is a graph showing the relative content of peak area according tomelting temperature (Tm) using SSA analysis according to one embodimentof the invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

As used herein, terms “a first”, “a second” and the like are used toexplain various constructional elements, and they are used only todistinguish one constructional element from other constructionalelements.

And, the terms used herein are only to explain specific embodiments, andare not intended to limit the present invention. A singular expressionincludes a plural expression thereof, unless it is expressly stated orobvious from the context that such is not intended. As used herein, theterms “comprise” or “have”, etc. are intended to designate the existenceof practiced characteristic, number, step, constructional element orcombinations thereof, and they are not intended to preclude thepossibility of existence or addition of one or more othercharacteristics, numbers, steps, constructional elements or combinationsthereof.

Although various modifications can be made to the present invention andthe present invention may have various forms, specific examples will beillustrated and explained in detail below. However, it should beunderstood that these are not intended to limit the present invention tospecific disclosure, and that the present invention includes all themodifications, equivalents or replacements thereof without departingfrom the spirit and technical scope of the invention.

Hereinafter, polyolefin according to the present invention will beexplained in detail. Polyolefin according to one embodiment of thepresent invention is characterized in that density is 0.915 g/cm³ to0.930 g/cm³; and the following requirements 1) to 3) are satisfied(provided that S₁+S₂+S₃=1) , when measuring the relative content of peakarea according to melting temperature (Tm) using SSA (SuccessiveSelf-nucleation and Annealing) analysis:

1) the content(S₁) of peak area at Tm less than 100° C. is 0.33 to 0.35;

2) the content(S₂) of peak area at Tm of 100° C. or more and 120° C. orless is 0.52 to 0.56; and

3) the content(S₃) of peak area at Tm greater than 120° C. is 0.10 to0.14.

Linear low density polyethylene(LLDPE) is prepared by copolymerizationof ethylene and alpha olefin at low pressure using a polymerizationcatalyst, and has narrow molecular weight distribution, and short chainbranch of a certain length. A linear low density polyethylene film hashigh breaking strength and elongation, excellent tear strength and dartdrop impact strength, as well as general properties of polyethylene, andthus, the use is increasing in stretch films, overlap films, and thelike, for which the existing low density polyethylene or high densitypolyethylene cannot be applied.

Meanwhile, it is known that as the density of linear low densitypolyethylene is lower, transparency and dart drop impact strengthincreases. However, if a lot of comonomers are used to prepare lowdensity polyethylene, fouling may be frequently generated in a slurrypolymerization process, and when preparing a film comprising the same,the amount of an antiblocking agent used should be increased due tostickiness. And, the production process may be unstable, or themorphology of produced polyethylene may be deteriorated, thus decreasingbulk density.

Thus, the present invention provides polyolefin that has optimum crystaldistribution capable of increasing transparency and dart drop impactstrength, by appropriately controlling the length and distribution ofethylene sequence forming lamella, and thus, controlling thedistribution of the areas of the melting peaks of crystals observed bySSA analysis.

Specifically, polyolefin according to one embodiment of the inventionhas density of 0.915 g/cm³ or more and 0.930 g/cm³ or less. Namely, itmay be low density polyolefin having density of 0.930 g/cm³ or less.

According to one embodiment of the invention, the polyolefin may be, forexample, copolymer of ethylene and alpha olefin. Wherein, the alphaolefin may include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene,ethylidene norbordene, phenyl norbordene, vinyl norbordene,dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene,styrene, alpha-methyl styrene, divinylbenzene, and 3-chloromethylstyrene. Among them, the polyolefin may be copolymer of ethylene and1-butene, copolymer of ethylene and 1-hexene, or copolymer of ethyleneand 1-octene.

More specifically, according to one embodiment, the density ofpolyolefin may be 0.915 g/cm³ or more, or 0.916 g/cm³ or more, or 0.917g/cm³ or more, or 0.918 g/cm³ or more, or, or 0.919 g/cm³ or more, and0.930 g/cm³ or less, or 0.928 g/cm³ or less, or 0.925 g/cm³ or less, or0.922 g/cm³ or less, or 0.921 g/cm³ or less, or 0.920 g/cm³ or less.Wherein the density is a value measured according to ASTM D1505.

According to one embodiment of the invention, the polyolefin ischaracterized by having specific peak area distribution, when measuringcrystals, i.e., peak area distribution, according to meltingtemperature(Tm), by stepwise SSA (Successive Self-nucleation andAnnealing) analysis.

The polyolefin of the present invention is semi-crystalline polymer, andmay include a crystalline part and an amorphous part. Specifically,polymer chains comprising ethylene repeat units or alpha olefin repeatunits are folded to make a bundle, thereby forming a crystallineblock(or segment) in the form of lamella.

The present invention is based on the discovery that polyolefinsatisfying following requirements 1) to 3) (provided that S₁+S₂+S₃=1) ,when measuring the relative content of peak area according to meltingtemperature (Tm) using SSA (Successive Self-nucleation and Annealing)analysis, may have improved transparency and dart drop impact strengthcompared to the existing polyolefin: 1) the content(S₁) of peak area atTm less than 100° C. is 0.33 to 0.35; 2) the content(S₂) of peak area atTm of 100° C. or more and 120° C. or less is 0.52 to 0.56; and 3) thecontent(S₃) of peak area at Tm greater than 120° C. is 0.10 to 0.14.

SSA (Successive Self-nucleation and Annealing) is a method of quenchingevery time each stage ends while decreasing temperature by stages usingDifferential Scanning Calorimeter(DSC), thereby preserving crystalscrystallized at the corresponding temperature every stage.

Specifically, if polyolefin is heated to completely molten, and then,cooled to a specific temperature(T) and gradually annealed, lamellaeunstable at the corresponding temperature(T) are still molten and onlystable lamellae are crystallized. Wherein, the stability to thecorresponding temperature(T) depends on the thickness of lamella, andthe thickness of lamella depends on the structure of chain. Thus, byprogressing heat treatment by stages, the thickness and distributiondegree of lamellae according to the structure of polymer chain can bemeasured quantitatively, and thus, distribution of each melting peakarea can be measured.

According to one embodiment of the invention, SSA may be conducted byheating the polyolefin to the first heating temperature of 120 to 124°C. using DSC, maintaining for 15 to 30 minutes, and then, cooling to 28to 32° C., and while decreasing heating temperature by stages with(n+1)th heating temperature being 3 to 7° C. lower than nth heatingtemperature, repeating heating-annealing-quenching until the finalheating temperature becomes 50 to 54° C.

More specifically, SSA may be conducted by the following steps i) to v):

i) heating polyolefin to 160° C. using DSC, and then, maintaining for 30minutes to remove all the heat history before measurement;

ii) decreasing temperature from 160° C. to 122° C., and then,maintaining for 20 minutes, decreasing temperature to 30° C., andmaintaining for 1 minute;

iii) heating to 117° C., which is 5° C. lower than 122° C., and then,maintaining for 20 minutes, decreasing temperature to 30° C., andmaintaining for 1 minute;

iv) while gradually decreasing the heating temperature at the identicaltemperature rise speed, maintenance time and cooling temperature, with(n+1)th heating temperature being 5° C. lower than nth heatingtemperature, repeating until the heating temperature becomes 52° C.; and

v) finally, increasing the temperature from 30° C. to 160° C.

The temperature profile of SSA analysis according to one embodiment ofthe invention is shown in FIG. 1.

Referring to FIG. 1, polyolefin is first heated to 160° C. usingdifferential scanning calorimeter(device name: DSC8000, manufacturingcompany: PerkinElmer), and then, maintained for 30 minutes to remove allthe heat history before measuring the sample. The temperature isdecreased from 160 t to 122° C., and then, maintained for 20 minutes,and decreased to 30° C. and maintained for 1 minute, and then, increasedagain.

Next, after heating to a temperature (117° C.) 5° C. lower than thefirst heating temperature of 122° C., the temperature is maintained for20 minutes, decreased to 30° C. and maintained for 1 minute, and then,increased again. In this way, while gradually decreasing the heatingtemperature at the identical maintenance time and cooling temperature,with (n+1)th heating temperature being 5° C. lower than nth heatingtemperature, the process is repeated till 52° C. Wherein, thetemperature increase speed and decrease speed are respectivelycontrolled to 20° C./min. Finally, in order to quantitatively analyzingthe distribution of crystals formed with repeatedheating-annealing-quenching, while raising the temperature from 30° C.to 160° C. at the temperature rise speed of 10° C./min, enthalpy changeis observed to measure thermogram.

As such, if heating-annealing-quenching of the polyolefin of the presentinvention are repeated by SSA method, peaks appear according totemperature, and therefrom, the relative content of peaks according tomelting temperature section can be calculated. Wherein, the relativecontent of peaks may be defined as the ratio of peak area atcorresponding melting temperature section(less than 100° C., 100° C. ormore and 120° C. or less, greater than 120 t) to the area of crystalmelting peaks at the entire temperature region.

When calculated by the above method, the polyolefin of the presentinvention exhibits the content(S₁) of peak areas at Tm less than 100°C., of 0.33 to 0.35; the content(S₂) of peak areas at Tm of 100° C. ormore and 120° C. or less, of 0.52 to 0.56; and the content(S₃) of peakareas at Tm greater than 120° C., of 0.10 to 0.14.

Since the polyolefin of the present invention has the above peak areadistribution according to melting temperature, it can realize excellentmechanical properties of a film such as dart drop impact strength, whilemaintaining low density of 0.930 g/cm³ or less and high transparency.

And, according to the polyolefin of the present invention, dart dropimpact strength equivalent to that of low density products can berealized, even by a product having higher density.

For example, the polyolefin film of the present invention having densityof 0.9195 g/cm³ or more and less than 0.9205 g/cm³ may exhibit dart dropimpact strength equivalent to that of the existing polyolefin havingdensity of 0.9175 g/cm³ or more and less than 0.9185 g/cm³. Thus,products can be produced with higher density to realize the same dartdrop impact strength, and thus, cost reduction due to productivityimprovement can be expected.

And, the polyolefin according to one embodiment of the invention mayhave melt index(MI_(2.16)) measured under temperature of 190° C. andload of 2.16 kg according to ASTM D1238 of 0.5 to 1.5 g/10 min, whilesatisfying the above explained properties. More specifically, the meltindex (MI2.16) may be 0.5 g/10 min or more, or 0.7 g/10 min or more, or0.8 g/10 min or more, or 0.9 g/10 min or more, and 1.5 g/10 min or less,or 1.4 g/10 min or less, or 1.3 g/10 min or less.

And, the polyolefin according to one embodiment of the invention mayhave dart drop impact strength of 850 g or more, or 900 g or more, or950 g or more, measured according to ASTM D 1709 [Method A], afterpreparing a polyolefin film(BUR 2.3, film thickness 55 to 65 μm) using afilm applicator. As the dart drop impact strength is higher, it is moreexcellent, and thus, the upper limit is not specifically limited, butfor example, it may be 1,500 g or less, or 1,400 g or less, or 1,300 gor less, or 1,200 g or less.

The polyolefin of the present invention may exhibit improved dart dropimpact strength, compared to the existing polyolefin having density ofthe same range.

For example, at a density of 0.9175 g/cm³ or more and less than 0.9185g/cm³, dart drop impact strength of the existing polyolefin is less than1,100 g, while the polyolefin of the present invention may exhibit dartdrop impact strength of 1,100 g or more, for example, 1,150 g to 1,400g.

And, at a density of 0.9185 g/cm³ or more and less than 0.9195 g/cm³,dart drop impact strength of the existing polyolefin is less than 850 g,while the polyolefin of the present invention may exhibit dart dropimpact strength of 850 g or more, for example, 900 g to 1,300 g.

And, at a density of 0.9195 g/cm³ or more and less than 0.9205 g/cm³,dart drop impact strength of the existing polyolefin is less than 800 g,while the polyolefin of the present invention may exhibit dart dropimpact strength of 800 g or more, for example, 850 g to 1,200 g.

And, the polyolefin according to one embodiment of the invention mayhave weight average molecular weight(Mw) of 70,000 to 140,000 g/mol.More preferably, the weight average molecular weight may be 80,000 g/molor more, or 90,000 g/mol or more, and 130,000 g/mol or less, or 120,000g/mol or less.

The weight average molecular weight(Mw) is measured using gel permeationchromatography(GPC), and it means universal calibration value using apolystyrene standard, and may be appropriately controlled consideringthe use or application field of the polyolefin.

Meanwhile, the polyolefin according to one embodiment of the inventionhaving the above described properties may be prepared by a methodcomprising a step of polymerizing olefin monomers in the presence of ahybrid supported metallocene compound as the catalytically activecomponent.

More specifically, the polyolefin of the present invention, although notlimited thereto, may be prepared by polymerizing olefin monomers in thepresence of a hybrid supported metallocene catalyst comprising one ormore first metallocene compounds selected from compounds represented bythe following Chemical Formula 1; one or more second metallocenecompounds selected from compounds represented by the following ChemicalFormula 2; and a carrier supporting the first and second metallocenecompounds.

in the Chemical Formula 1,

Q₁ and Q₂ are identical to or different from each other, and eachindependently, halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, aC2-C20 alkoxyalkyl group, a C6-C20 aryl group, a C7-C20 alkylaryl group,or a C7-C20 arylalkyl group;

T₁ is carbon, silicon or germanium;

M₁ is a Group 4 transition metal;

X₁ and X₂ are identical to or different from each other, and eachindependently, halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, aC6-C20 aryl group, a nitro group, an amido group, a C1-C20 alkylsilylgroup, a C1-C20 alkoxy group, or a C1-C20 sulfonate group;

R₁ to R₁₄ are identical to or different from each other, and eachindependently, hydrogen, halogen, a C1-C20 alkyl group, a C1-C20haloalkyl group, a C2-C20 alkenyl group, a C1-C20 alkylsilyl group, aC1-C20 silylalkyl group, a C1-C20 alkoxysilyl group, a C1-C20 alkoxygroup, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20arylalkyl group, or two or more neighboring groups of R₁ to R₁₄ areconnected with each other to form a substituted or unsubstitutedaliphatic or aromatic ring;

in the Chemical Formula 2,

Q₃ and Q₄ are identical to or different from each other, and eachindependently, halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, aC2-C20 alkoxyalkyl group, a C6-C20 aryl group, a C7-C20 alkylaryl group,or a C7-C20 arylakyl group;

T₂ is carbon, silicon or germanium;

M₂ is a Group 4 transition metal;

X₃ and X₄ are identical to or different from each other, and eachindependently, halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, aC6-C20 aryl group, a nitro group, an amido group, a C1-C20 alkylsilylgroup, a C1-C20 alkoxy group, or a C1-C20 sulfonate group;

R₁₅ to R₂₈ are identical to or different from each other, and eachindependently, hydrogen, halogen, a C1-C20 alkyl group, a C1-C20haloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkoxyalkyl group, aC1-C20 alkylsilyl group, a C1-C20 silylalkyl group, a C1-C20 alkoxysilylgroup, a C1-C20 alkoxy group, a C6-C20 aryl group, a C7-C20 alkylarylgroup, or a C7-C20 arylalkyl group, provided that R₂₀ and R₂₄ areidentical to or different from each other, and each independently, a C1to C20 alkyl group, or two or more neighboring groups of R₁₅ to R₂₈ areconnected with each other to form a substituted or unsubstitutedaliphatic or aromatic ring.

In the hybrid supported metallocene catalyst, the substituents of theChemical Formulas 1 and 2 will be explained in detail.

The C1 to C20 alkyl group may include a liner or branched alkyl group,and specifically, may include a methyl group, an ethyl group, a propylgroup, an isopropyl group, an n-butyl group, a tert-butyl group, apentyl group, a hexyl group, a heptyl group, an octyl group, and thelike, but is not limited thereto.

The C2 to C20 alkenyl group may include a linear or branched alkenylgroup, and specifically, may include an allyl group, an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, and the like, but isnot limited thereto.

The C6 to C20 aryl group may include a monocyclic or condensed ring arylgroup, and specifically, it may include a phenyl group, a biphenylgroup, a naphthyl group, a phenanthrenyl group, a fluorenyl group, andthe like, but is not limited thereto.

The C1 to C20 alkoxy group may include a methoxy group, an ethoxy group,a phenyloxy group, a cyclohexyloxy group, and the like, but is notlimited thereto.

The C2 to C20 alkoxyalkyl group is a functional group wherein one ormore hydrogen atoms of the above explained alkyl group are substitutedwith an alkoxy group, and specifically, it may include an alkoxyalkylgroup such as a methoxymethyl group, a methoxyethyl group, anethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethylgroup, an iso-propoxyhexyl group, a tert-butoxymethyl group, atert-butoxyethyl group, a tert-butoxyhexyl group, and the like; or anaryloxyalkyl group such as a phenoxyhexyl group, and the like, but isnot limited thereto.

The C1 to C20 alkylsilyl group or C1 to C20 alkoxysilyl group is afunctional group wherein 1 to 3 hydrogen atoms of —SiH₃ are substitutedwith the above explained alkyl group or alkoxy group, and specifically,may include an alkylsilyl group such as a methylsilyl group, adimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group,a diethylmethylsilyl group or a dimethylpropylsilyl group; analkoxysilyl group such as a methoxysilyl group, a dimethoxysilyl group,a trimethoxy silyl group or a dimethoxyethoxysilyl group, and the like;an alkoxyalkylsilyl group such as a methoxydimethylsilyl group, adiethoxymethylsilyl group, or a dimethoxypropylsilyl group, and thelike, but is not limited thereto.

The C1 to C20 silylalkyl is a functional group wherein one or morehydrogen atoms of the above explained alkyl group are substituted with asilyl group, and specifically, may include —CH₂—SiH₃, amethylsilylmethyl group, or a dimethylethoxysilylpropyl group, and thelike, but is not limited thereto.

The halogen may be fluorine(F), chlorine(Cl), bromine(Br), or iodine(I).

The sulfonate group has a structure of —O—SO₂—R′ wherein R′ may be aC1-C20 alkyl group. Specifically, the C1 to C20 sulfonate group mayinclude a methanesulfonate group or a phenylsulfonate group, and thelike, but is not limited thereto.

And, as used herein, the description “two neighboring substituents areconnected with each other to form an aliphatic or aromatic ring” meansthat atom(s) of two substituents and atom(s) to which the twosubstituents bond are connected with each other to form a ring.Specifically, as the examples of the case wherein R_(a) and R_(b) orR_(a′) and R_(b′) of —NR_(a)R_(b) or —NR_(a)R_(b′) are connected witheach other to form an aliphatic ring, a piperidinyl group, and the likemay be mentioned, and as the example of the case wherein R_(a) and R_(b)or R_(a′) and R_(b′) of —NR_(a)R_(b) or —NR_(a′)R_(b′) are connectedwith each other to form an aromatic ring, a pyrrolyl group, and the likemay be mentioned.

The above explained substituents may be optionally substituted with oneor more substituents selected from the group consisting of a hydroxylgroup; halogen; an alkyl group or an alkenyl group, an aryl group, analkoxy group; an alkyl group or an alkenyl group, an aryl group, analkoxy group including one or more hetero atoms of Group 14 to Group 16;a silyl group; an alkylsilyl group or an alkoxysilyl group; a phosphinegroup; a phosphide group; a sulfonate group; and a sulfone group.

As the Group 4 transition metal, titanium(Ti), zirconium(Zr),hafnium(Hf), and the like may be mentioned, but is not limited thereto.

Using the hybrid supported catalyst, excellent dart drop impact strengthmay be secured by specific melting peak distribution, while maintainingtransparency of polyolefin, and thus, polyolefin having highprocessability, particularly excellent melt blown processability may beprepared.

Specifically, in the hybrid supported catalyst according to oneembodiment of the invention, the first metallocene compound compriseslong chain branches and is easy to prepare low molecular weightpolyolefin, and the second metallocene compound comprises a small amountof long chain branches compared to the first metallocene compound and iseasy to prepare relatively high molecular weight polyolefin.Particularly, when polymer comprises a lot of long chain branches andhas large molecular weight, the melt strength increases, but the firstmetallocene compound comprises a lot of long chain branches but has lowmolecular weight, there is a limit in improving bubble stability.

In the present invention, a first metallocene compound comprisingrelatively many long chain branches and producing low molecular weightpolymer, and a second metallocene compound comprising relatively manyshort chain branches and producing high molecular weight polymer aresupported together, thereby maintaining excellent transparency andimproving melt strength. By supporting the two kinds of metallocenecompounds together, long chain branches existing in the polymer arepositioned relatively toward low molecular weight, and thus,transparency is not deteriorated.

Particularly, the hybrid supported catalyst of the present invention ischaracterized in that long chain branches produced by the firstmetallocene compound of the Chemical Formula 1 and long chain branchesproduced by the second metallocene compound of the Chemical Formula 2are entangled with each other in a molecular level. Due to theentanglement between long chain branches, a large force is required torelease a molten state. Seeing that melt strength is not improved whenmelt blending homopolymers produced by each catalyst, improvement inmelt strength is effective when entanglement occurs from thepolymerization step by the hybrid supported catalyst.

More specifically, in the hybrid supported catalyst according to oneembodiment of the invention, the first metallocene compound representedby the Chemical Formula 1 comprises a cyclopentadienyl ligand and atetrahydroindenyl ligand, wherein the ligands are cross-linked by—Si(Q₁)(Q₂)-, and M₁(X₁)(X₂) exists between the ligands. By polymerizingwith the catalyst having such a structure, polymer comprising a smallamount of long chain branches, and relatively narrow molecular weightdistribution (PDI, MWD, Mw/Mn) and melt flow rate ratio(MFRR) may beobtained.

Specifically, in the structure of the metallocene compound representedby the Chemical Formula 1, the cyclopentadienyl ligand may have aninfluence on olefin polymerization activity, for example.

Particularly, in case R₁₁ to R₁₄ of the cyclopentadineyl ligand are eachindependently, a C1 to C20 alkyl group, a C1 to C20 alkoxy group, or aC2 to C20 alkenyl group, a catalyst obtained from the metallocenecompound of the Chemical Formula 1 may exhibit higher activity during anolefin polymerization process, and in case R₁₁ to R₁₄ are eachindependently, a methyl group, an ethyl group, a propyl group, or abutyl group, the hybrid supported catalyst may exhibit higher activityduring the polymerization process of olefin monomers.

And, the metallocene compound represented by the Chemical Formula 1 hasunshared electron pairs capable of acting as Lewis base to thetetrahydroindenyl ligand, thereby exhibiting stable and highpolymerization activity, and the tetrahydroindenyl ligand may controlthe degree of steric hindrance effect according to the kind ofsubstituted functional groups, thus easily controlling the molecularweight of prepared polyolefin.

Specifically, in the Chemical Formula 1, R₁ may be hydrogen, a C1 to C20alkyl group, a C1 to C20 alkoxy group, or a C2 to C20 alkenyl group.More specifically, in the Chemical Formula 1, R₁ may be hydrogen or a C1to C20 alkyl group, and R₂ to R₁₀ may be each independently, hydrogen.In this case, the hybrid supported catalyst may provide polyolefinhaving excellent processability.

And, in the structure of the metallocene compound represented by theChemical Formula 1, the cyclopentadienyl ligand and tetrahydroindenylligand are cross-linked by —Si(Q₁)(Q₂)-, thus exhibiting excellentstability. In order to secure the effect more effectively, Q₁ and Q₂ maybe each independently, a C1 to C20 alkyl group, or a C6 to C20 arylgroup. More specifically, a metallocene compound wherein Q₁ and Q₂ areeach independently, a methyl group, an ethyl group, an n-propyl group,an iso-propyl group, an n-butyl group, a t-butyl group, a phenyl group,or a benzyl group, may be used.

In the structure of the metallocene compound represented by the ChemicalFormula 1, M₁(X₁)(X₂) existing between the cyclopentadienyl ligand andtetrahydroindenyl ligand may have an influence on the storage stabilityof metal complex. In order secure the effect more effectively, X₁ and X₂may be each independently, halogen, a C1 to C20 alkyl group, or a C1 toC20 alkoxy group. More specifically, X₁ and X₂ may be eachindependently, F, Cl, Br or I, and Mi may be Ti, Zr or Hf; Zr or Hf; orZr.

For example, as the first metallocene compound capable of providingpolyolefin exhibiting more improved dart drop impact strength and highshort chain branch content and having excellent blown filmprocessability, compounds represented by the following structuralformulas may be mentioned, but not it is limited thereto.

The first metallocene compound represented by the Chemical Formula 1 maybe synthesized applying known reactions. Specifically, it may beprepared by connecting between tetrahydroindenyl derivative andcyclopentadiene derivative by a bridge compound to prepare a ligandcompound, and then, introducing a metal precursor compound to conductmetallation, but the method is not limited thereto, and for moredetailed synthesis method, examples may be referred to.

Meanwhile, in the hybrid supported catalyst according to one embodimentof the invention, the metallocene compound represented by the ChemicalFormula 2 has different ligands of a cyclopentadienyl ligand and anindenyl ligand having substituents(R₂₀ and R₂₄) at specific positions,wherein the different ligands are cross-linked by —Si(Q₃)(Q₄)-, andM₂(X₃)(X₄) exists between the different ligands. If the metallocenecompound having such a specific structure is activated by an appropriatemethod and used as a catalyst for olefin polymerization reaction, longchain branches can be produced. As such, by introducing substituents(R₂₀and R₂₄) at specific positions of the indene derivative of the ChemicalFormula 2, the metallocene compound may have high polymerizationactivity, compared to metallocene compounds comprising unsubstitutedindene compound or indene compound substituted at another position.

Particularly, the second metallocene compound represented by theChemical Formula 2, by homopolymerization, has molecular weight of about150,000 to 550,000 and has SCB, and thus, when applied for a hybridcatalyst, has narrow molecular weight distribution and improveprocessability.

Specifically, in the structure of the metallocene compound representedby the Chemical Formula 2, the cyclopentadienyl ligand may have aninfluence on the olefin polymerization activity.

Particularly, in case R₂₅ to R₂₈ of the cyclopentadineyl ligand are eachindependently, hydrogen, a C1 to C20 alkyl group, a C2 to C20alkoxyalkyl group, or a C6 to C20 aryl group, a catalyst obtained fromthe metallocene compound of the Chemical Formula 2 may exhibit higheractivity during an olefin polymerization process, and in case R₂₅ andR₂₈ are each independently, hydrogen, a C1 to C20 alkyl group, or a C2to C20 alkoxyalkyl group, the hybrid supported catalyst may exhibit veryhigh activity during the polymerization process of olefin monomers.

And, in the structure of the metallocene compound represented by theChemical Formula 2, the indenyl ligand may control the degree of sterichindrance effect according to the kind of substituted functional groups,thus easily controlling the molecular weight of prepared polyolefin.

Specifically, in order to increase molecular weight, it is preferablethat a phenyl group is substituted at the 4^(th) position of the indenylgroup, R₂₀ at the para-position of the phenyl group is a C1 to C20 alkylgroup, and R₂₄, the substituent at the 6^(th) position of the indenylgroup is a C1 to C20 alkyl group. Particularly, R₂₀ and R₂₄ may be eachindependently, a C1 to C4 alkyl group, R₂₀ may be preferably a methylgroup, an ethyl group, an n-propyl group, an iso-propyl group, and thelike, and R₂₄ may be preferably a t-butyl group. In this case, thehybrid supported catalyst can provide polyolefin having excellentcomonomer incorporation.

The remaining substituents of the indenyl group, R₁₅ to R₁₉ and R₂₁ toR₂₃ may be each independently, hydrogen, halogen, a C1 to C20 alkylgroup, a C1 to C20 haloalkyl group, a C2 to C20 alkenyl group, a C2 toC20 alkoxyalkyl group, a C1 to C20 alkylsilyl group, a C1 to C20silylalkyl group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxygroup, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 toC20 arylalkyl group.

And, in the structure of the metallocene compound represented by theChemical Formula 2, the cyclopentadienyl ligand and indenyl ligand arecross-linked by —Si(Q₃)(Q₄)-, thus exhibiting excellent stability. Inorder to secure the effect more effectively, Q₃ and Q₄ may be eachindependently, a C1 to C20 alkyl group or a C2 to C20 alkoxyalkyl group.More specifically, a metallocene compound wherein Q₃ and Q₄ are eachindependently, a methyl group, an ethyl group, an n-propyl group, aniso-propyl group, an n-butyl group, a t-butyl group, a methoxymethylgroup, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethylgroup, an iso-propoxyethyl group, an iso-propoxyhexyl group, atert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexylgroup may be used.

Particularly, in the metallocene compound represented by the ChemicalFormula 2, one or more of the substituents of the cyclopentadiene(Cp) or—Si(Q₃)(Q₄)-silyl group may be a C2 to C20 alkoxyalkyl group, morepreferably, an iso-propoxyethyl group, an iso-propoxyhexyl group, atert-butoxyethyl group, a tert-butoxyhexyl group, and the like.

The C2 to C20 alkoxyalkyl group may have an influence on the comonomerincorporation of alpha olefin comonomers such as 1-butene or 1-hexene,and in case the alkoxyalkyl group has a short alkyl group chain of C4 orless, comonomer incorporation of alpha olefin comonomers may be loweredwhile maintaining total polymerization activity, and thus, polyolefinwith controlled comonomer incorporation can be prepared withoutdeterioration of other properties.

And, in the structure of the metallocene compound represented by theChemical Formula 2, M₂(X₃)(X₄) existing between the cyclopentadienylligand and indenyl ligand may have an influence on storage stability ofmetal complex. In order to secure the effect more effectively, X₃ and X₄may be each independently, halogen, a C1 to C20 alkyl group, or a C1 toC20 alkoxy group. More specifically, X₃ and X₄ may be eachindependently, F, CI, Br or I, and M₂ may be Ti, Zr or Hf; Zr or Hf; or,Zr.

Meanwhile, as specific examples of the second metallocene compoundrepresented by the Chemical Formula 2, compounds represented by thefollowing structural formulas may be mentioned, but the presentinvention is not limited thereto.

As explained, since the hybrid supported metallocene catalyst of oneembodiment comprises the first and second metallocene compounds, it canprepare polyolefin having excellent processability and properties,particularly, excellent dart drop impact strength.

Particularly, the mole ratio of the first metallocene compound and thesecond metallocene compound may be about 1.2:1 to 7.5:1, preferablyabout 1.5:1 to 7.0:1, more preferably 1.8:1 to 6.5:1. The mixing moleratio of the first metallocene compound and the second metallocenecompound may be 1.2:1 or more so as to control molecular weight and theamount of SCB, LCB to fulfill both properties and processability, and itmay be 7.5:1 or less so as to secure processability.

Meanwhile, since the first and second metallocene compounds have theabove explained structural characteristics, they can be stably supportedin a carrier.

As the carrier, carriers containing hydroxyl groups or siloxane groupson the surface may be used. Specifically, as the carrier, those dried athigh temperature to remove moisture on the surface, thus containinghighly reactive hydroxyl groups or siloxane groups may be used. Morespecifically, as the carrier, silica, alumina, magnesia or a mixturethereof may be used, and among them, silica may be more preferable. Thecarrier may be dried at high temperature, and for example, hightemperature dried silica, silica-alumina, or silica-magnesia, and thelike may be used, which may commonly comprise oxide, carbonate, sulfate,nitrate components such as Na₂O, K₂CO₃, BaSO₄ and Mg(NO₃)₂, and thelike.

The drying temperature of the carrier may be preferably about 200 to800° C., more preferably about 300 to 600° C., and most preferably about300 to 400° C. If the drying temperature of the carrier is less thanabout 200° C., surface moisture may react with a cocatalyst, and if itis greater than about 800° C., pores on the surface of the carrier maybe combined to decrease surface area, and surface hydroxyl groups maydisappear to remain only siloxane groups, and thus, reaction sites witha cocatalyst may decrease.

The amount of hydroxyl groups on the surface of the carrier may bepreferably about 0.1 to 10 mmol/g, and more preferably, about 0.5 to 5mmol/g. The amount of hydroxyl groups on the surface of the carrier maybe controlled by the preparation method and conditions or dryingconditions of the carrier, for example, temperature, time, vacuum orspray drying, and the like.

If the amount of hydroxy groups is less than about 0.1 mmol/g, reactionsites with a cocatalyst may be few, and if it is greater than about 10mmol/g, they may be derived from moisture other than hydroxy groupsexisting on the surface of the carrier particles, which is notpreferable.

And, in the hybrid supported metallocene catalyst of one embodiment, acocatalyst supported together on the carrier so as to activate themetallocene compound is not specifically limited as long as it is anorganic metal compound including Group 13 metal and can be used forolefin polymerization in the presence of common metallocene catalyst.

Specifically, the cocatalyst compound may comprise one or more of analuminum-containing first cocatalyst of the following Chemical Formula3, and a borate-based second cocatalyst of the following ChemicalFormula 4

R_(a)—[Al(R_(b))—O]_(n)—R_(c)   [Chemical Formula 3]

In the Chemical Formula 3,

R_(a), R_(b), and R_(c) are identical to or different from each other,and each independently, hydrogen, halogen, a C1 to C20 hydrocarbylgroup, or a C1 to C20 hydrocarbyl group substituted with halogen;

n is an integer of 2 or more;

T⁺[BG₄]⁻  [Chemical Formula 4]

In the Chemical Formula 4, T⁺ is +1 valent polyatomic ion, B is boron in+3 oxidation state, G's are each independently, selected from the groupconsisting of a hydride group, a dialkylamido group, a halide group, analkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbylgroup and a halo-substituted hydrocarbyl group, and G has 20 or lesscarbon, provided that G is a halide group at one or less position.

The first cocatalyst of the Chemical Formula 3 may be analkylaluminoxane-based compound in which repeat units bond in linear,circular or network shape, and specific examples of the first cocatalystmay include methylaluminoxane(MAO), ethylalulminoxane,isobutylaluminoxane, or butylaluminoxane, and the like.

And, the second cocatalyst of the Chemical Formula 4 may be aborate-based compound in the form of tri-substituted ammonium salt, ordialkyl ammonium salt, or tri-substituted phosphonium salt. As specificexamples of the second cocatalyst, a borate-based compounds in the formof tri-substituted ammonium salt, such as trimethylammoniumtetraphenylborate, methyldioctadecylammonium tetraphenylborate,triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate,tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclooctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate,N,N-diethylanilinium tetraphenylborate,N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate,trimethylammonium tetrakis(pentafluorophenyl)borate,methylditetradecylammonium tetrakis(pentafluorophenyl)borate,methyldioctadecylammonium tetrakis(pentafluorophenyl)borate,triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammoniumtetrakis (pentafluorophenyl)borate, tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethyl(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate,N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, andN,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate;a borate-based compound in the form of dialkylammonium salt, such asdioctadecylammonium tetrakis(pentafluorophenyl)borate,ditetradecylammonium tetrakis(pentafluorophenyl)borate anddicyclohexylammonium tetrakis(pentafluorophenyl)borate; and aborate-based compound in the form of trisubstituted phosphonium salt,such as triphenylphosphonium tetrakis(pentafluorophenyl)borate,methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate andtri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate,may be mentioned.

In the hybrid supported metallocene catalyst of one embodiment, the massratio of total transition metal included in the first metallocenecompound and the second metallocene compound and the carrier may be 1:10to 1:1000. When the carrier and the metallocene compounds are includedat the above mass ratio, optimum shape may be exhibited.

And, the mass ratio of the cocatalyst compound and the carrier may be1:1 to 1:100. When the cocatalyst and the carrier are included at theabove mass ratio, activity and polymer fine structure may be optimized.

The hybrid supported metallocene catalyst of one embodiment may be usedfor the polymerization of olefin monomers. And, the hybrid supportedmetallocene catalyst may be subjected to a contact reaction with olefinmonomers and prepared as a pre-polymerized catalyst, and for example,the catalyst may be separately contacted with olefin monomers such asethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like andprepared as a pre-polymerized catalyst.

Meanwhile, the hybrid supported metallocene catalyst of one embodimentmay be prepared by a method comprising steps of supporting a cocatalyston a carrier; and supporting the first and second metallocene compoundson the carrier where the cocatalyst is supported.

Wherein, the first and second metallocene compounds may be sequentiallysupported one by one, or two kinds may be supported together. Thesequence of supporting is not limited, but the second metallocenecatalyst having relatively poor morphology may be supported first toimprove the shape of the hybrid supported metallocene catalyst, andthus, after supporting the second metallocene catalyst, the firstmetallocene catalyst may be sequentially supported.

In the above method, supporting conditions are not specifically limited,and it may be conducted under conditions well known to a person havingordinary knowledge in the art. For example, high temperature supportingand low temperature supporting may be appropriately used, and forexample, the supporting temperature may be about −30° C. to 150° C.,preferably room temperature(about 25° C.) to about 100° C., morepreferably room temperature to about 80° C. The supporting time may beappropriately controlled according to the amount of the metallocenecompounds to be supported. The reacted supported catalyst may be used asit is, after filtering or vacuum distilling a reaction solvent toremove, and if necessary, it may be soxhlet filtered with aromatichydrocarbon such as toluene.

And, the supported catalyst may be prepared under solvent ornon-solvent. As the solvent that can be used, aliphatic hydrocarbonsolvents such as hexane or pentane, aromatic hydrocarbon solvents suchas toluene or benzene, hydrocarbon solvents substituted with chlorineatom such as dichloromethane, ether-based solvents such as diethyletheror THF, acetone, ethylacetate, and the like may be mentioned, andhexane, heptanes, toluene or dichloromethane may be preferably used.

Meanwhile, according to another embodiment of the invention, a methodfor preparing polyolefin comprising a step of polymerizing olefinmonomers in the presence of the hybrid supported metallocene catalyst isprovided.

And, the olefin monomers may be one or more selected from the groupconsisting of ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosens, norbornene,norbornadiene, ethylidene norbordene, phenyl norbordene, vinylnorbordene, dicylcopentadiene, 1,4-butadiene, 1,5-pentadiene,1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and3-chloromethyl styrene.

For the polymerization reaction of olefin monomers, variouspolymerization processes known as the polymerization reaction of olefinmonomers, such as continuous solution polymerization, bulkpolymerization, suspension polymerization, slurry polymerization oremulsion polymerization, and the like, may be used. The polymerizationreaction may be conducted at a temperature of about 25 to 500° C., orabout 25 to 200° C., or about 50 to 150° C., under pressure of about 1to 100 bar or about 10 to 80 bar.

And, in the polymerization reaction, the hybrid supported metallocenecatalyst may be used while dissolved or diluted in a solvent such aspentane, hexane, heptanes, nonane, decane, toluene, benzene,dichloromethane, chlorobenzene, and the like. Wherein, the solvent maybe treated with a small amount of alkylaluminum to remove a small amountof water or air that may have an adverse influence on the catalyst.

And, the polyolefin prepared by the above method may exhibit high dartdrop impact strength, as well as low density, and excellenttransparency.

Specifically, the polyolefin may exhibit melt index(MI_(2.16)) measuredunder temperature of 190° C. and load of 2.16 kg according to ASTMD1238, of 0.5 to 1.5 g/10 min.

And, the polyolefin may exhibit haze of a film of 12% or less, measuredaccording to ISO 13468, after preparing a polyolefin film(BUR 2.3, filmthickness 55 to 65 μm) using a film applicator.

And, the polyolefin may exhibit dart drop impact strength of 850 g ormore, measured according to ASTM D 1709 [Method A], after preparing apolyolefin film(BUR 2.3, film thickness 55 to 65 μm) using a filmapplicator.

And, in case the polyolefin is, for example, ethylene-alpha olefincopolymer, preferably copolymer of ethylene and 1-butene, or copolymerof ethylene and 1-hexene, the above properties may be more appropriatelyfulfilled.

Hereinafter, preferable examples are presented for better understandingof the invention. However, these examples are presented only as theillustrations of the invention and the scope of the present invention isnot limited thereby.

EXAMPLE Synthesis Example 1 A First Metallocene Compound

1-1 Preparation of a Ligand Compound

Tetramethylcyclopentadiene(TMCP) was lithiated with n-BuLi(1 equivalent)in THF(0.4 M), and then, filtered and used as tetramethylcyclopentyl-Lisalts (TMCP-Li salts). Indene was lithiated with n-BuLi(1 equivalent) inhexane(0.5 M), and then, filtered and used as indene-Li salts(Ind-Lisalts). Into a 250 mL Schlenk flask, 50 mmol oftetramethylcyclopentyl-Li salts (TMCP-Li salts) and 100 mL oftetrahydrofurane(THF) were introduced under Ar. 1 equivalent ofdichloromethyl-(iso-propyl) silane was added at −20° C. After about 6hours, 3 mol % of CuCN and Ind-Li salts (50 mmol, MTBE 1M solution) wereadded at −20° C., and reacted for about 12 hours. An organic layer wasseparated with water and hexane to obtain ligand.

1-2 Preparation of a Metallocene Compound

Into a dried 250 mL Schlenk flask, 50 mmol of the ligand compoundsynthesized in 1-1 was introduced and dissolved in about 100 mL of MTBEunder Ar, and 2 equivalents of n-BuLi was added dropwise at −20° C.After reaction for about 16 hours, the ligand-Li solution was added toZrCl₄(THF)₂ (50 mmol, MTBE 1 M solution). After reaction for about 16hours, the solvent was removed, the reaction mixture was dissolved inmethylenechloride(MC) and filtered to remove LiCl. The solvent offiltrate was removed, about 50 mL of MTBE and about 100 mL of hexanewere added, and the solution was stirred for about 2 hours, and then,filtered to obtain a solid metallocene catalyst precursor.

Into a high pressure stainless steel(sus) reactor, the obtainedmetallocene catalyst precursor(20 mmol), 60 mL of DCM, and 5 mol % ofPd/C catalyst were introduced under argon atmosphere. Argon inside ofthe high pressure reactor was replaced with hydrogen three times, andhydrogen was filled such that pressure became about 20 bar. By stirringat 35° C. for about 24 hours, the reaction was completed. The inside ofthe reactor was replaced with argon, and then, the DCM solution wastransferred to a schlenk flask under argon atmosphere. The solution waspassed through celite under argon to remove the Pd/C catalyst, and thesolvent was dried to obtain a solid catalyst precursor.

¹H NMR (500 MHz, C6D6): 0.62 (3H, s), 0.98 (3H, d), 1.02 (3H, d), 1.16(2H, dd), 1.32-1.39 (3H, m), 1.78 (3H, s), 1.81 (3H, s), 1.84-1.94 (3H,m), 2.01 (3H, s), 2.03 (1H, m), 2.04 (3H, s), 2.35 (2H, m), 2.49-2.55(1H, m), 3.13-3.19 (1H, m), 5.27 (1H, d), 6.75 (1H, d).

Synthesis Example 2 A First Metallocene Compound

2-1 Preparation of a Ligand Compound

Tetramethylcyclopentadiene(TMCP) was lithiated with n-BuLi(1 equivalent)in THF(0.4 M), and then, filtered and used as tetramethylcyclopentyl-Lisalts (TMCP-Li salts). Indene was lithiated with n-BuLi(1 equivalent) inhexane(0.5 M), and then, filtered and used as indene-Li salts(Ind-Lisalts). Into a 250 mL Schlenk flask, 50 mmol oftetramethylcyclopentyl-Li salts (TMCP-Li salts) and 100 mL oftetrahydrofurane(THF) were introduced under Ar. 1 equivalent ofdichloromethylphenyl silane was added at −20° C. After about 6 hours, 3mol % of CuCN and Ind-Li salts (50 mmol, MTBE 1M solution) were added at−20° C., and reacted for about 12 hours. An organic layer was separatedwith water and hexane to obtain ligand.

2-2 Preparation of a Metallocene Compound

Into a dried 250 mL Schlenk flask, 50 mmol of the ligand compoundsynthesized in 2-1 was introduced and dissolved in about 100 mL of MTBEunder Ar, and 2 equivalents of n-BuLi was added dropwise at −20° C.After reaction for about 16 hours, the ligand-Li solution was added toZrCl₄(THF)₂ (50 mmol, MTBE 1 M solution). After reaction for about 16hours, the solvent was removed, the reaction mixture was dissolved inmethylenechloride(MC) and filtered to remove LiCl. The solvent offiltrate was removed, about 50 mL of MTBE and about 100 mL of hexanewere added, and the solution was stirred for about 2 hours, and then,filtered to obtain a solid metallocene catalyst precursor.

Into a high pressure stainless steel(sus) reactor, the obtainedmetallocene catalyst precursor(20 mmol), 60 mL of DCM, and 5 mol % ofPd/C catalyst were introduced under argon atmosphere. Argon inside ofthe high pressure reactor was replaced with hydrogen three times, andhydrogen was filled such that pressure became about 20 bar. By stirringat 35° C. for about 24 hours, the reaction was completed. The inside ofthe reactor was replaced with argon, and then, the DCM solution wastransferred to a schlenk flask under argon atmosphere. The solution waspassed through celite under argon to remove the Pd/C catalyst, and thesolvent was dried to obtain different stero isomers of metallocenecompound(A, B forms) at a ratio of 1.3:1.

¹H NMR (500 MHz, CDCl₃):

Form A: 0.88 (3H, s), 1.43-1.50 (1H, m), 1.52-1.57 (1H, m), 1.60 (3H,s), 1.62-1.68 (1H, m), 1.87-1.95 (1H, m), 1.95-2.00 (1H, m), 2.00 (3H,s), 2.06 (3H, s), 2.08 (3H, s), 2.41-2.47 (1H, m), 2.72-2.78 (1H, m),3.04-3.10 (1H, m), 5.62 (1H, d), 6.73 (1H, d), 7.49 (3H, m), 7.87 (2H,m)

Form B: 0.99 (3H, s), 1.42 (3H, s), 1.60-1.67 (2H, m), 1.90-1.98 (1H,m), 1.95 (3H, s), 2.06 (3H, s), 2.06-2.10 (1H, m), 2.11 (3H, s),2.44-2.49 (1H, m), 2.66-2.70 (1H, m), 2.74-2.79 (1H, m), 3.02-3.11 (1H,m), 5.53 (1H, d), 6.74 (1H, d), 7.48 (3H, m), 7.88 (2H, m).

Synthesis Example 3 A First Metallocene Compound

3-1 Preparation of a Ligand Compound

In a dried 250 mL schlenk flask, tetramethylcyclopentadiene (TMCP, 6.0mL, 40 mmol) was dissolved in THF (60 mL), and then, the solution wascooled to −78° C. Subsequently, n-BuLi (2.5M, 17 mL, 42 mmol) was slowlyadded dropwise to the solution, and then, the obtained solution wasstirred at room temperature overnight.

Meanwhile, in a separate 250 mL schlenk flask, dichlorodimethylsilane(4.8 mL, 40 mmol) was dissolved in n-hexane, and then, the solution wascooled to −78° C. Subsequently, the TMCP-lithiation solution preparedabove was slowly added to the solution. And, the obtained solution wasstirred at room temperature overnight. Thereafter, the obtained solutionwas decompressed to remove solvents. And, the obtained solid wasdissolved in toluene and filtered to remove remaining LiCl, thusobtaining an intermediate (yellow liquid, 7.0 g, 33 mmol, 83% yield).

¹H NMR (500 MHz, CDCl₃): 0.24 (6H, s), 1.82 (6H, s), 1.98 (6H, s), 3.08(1H, s).

In a dried 250 mL schlenk flask, indene (0.93 mL, 8.0 mmol) wasdissolved in THF (30 mL), and then, the solution was cooled to −78° C.Subsequently, n-BuLi (2.5M, 3.4 mL, 8.4 mmol) was slowly added dropwiseto the solution, and then, the obtained solution was stirred at roomtemperature for about 5 hours.

Meanwhile, in a separate 250 mL schlenk flask, the intermediatesynthesized above(1.7 g, 8.0 mmol) was dissolved in THF, and thesolution was cooled to −78° C. Subsequently, the indene-lithiationsolution prepared above was slowly added to the solution. And, theobtained solution was stirred at room temperature overnight to obtain areddish purple solution.

Thereafter, water was poured into the reactor to finish thereaction(quenching), and an organic layer was extracted with ether fromthe mixture. It was confirmed through ¹H NMR thatdimethyl(indenyl)(tetramethylcyclopentadienyl)silane and different kindsof organic compounds are included in the organic layer. The organiclayer was concentrated without purification and used for metallation.

3-2 Preparation of a Metallocene Compound

Into a 250 mL schlenk flask,dimethyl(indenyl)(tetramethylcyclopentadienyl)silane synthesized above(1.7 g, 5.7 mmol) was dissolved in toluene (30 mL) and MTBE (3.0 mL).And, the solution as cooled to −78° C., n-BuLi (2.5M, 4.8 mL, 12mmol)was slowly added dropwise to the solution, and the obtained solution wasstirred at room temperature overnight. However, yellow solid wasproduced in the solution and was not uniformly stirred, and thus, MTBE(50 mL) and THF (38 mL) were additionally introduced. Meanwhile, in aseparate 250 mL schlenk flask, ZrCl₄(THF)₂ was dispersed in toluene, andthe obtained mixture was cooled to −78° C. Subsequently, the lithiatedligand solution prepared above was slowly introduced into the mixture.And, the obtained mixture was stirred overnight.

Thereafter, the reaction product was filtered to obtain yellow solid(1.3g, containing LiCl (0.48 g), 1.8 mmol), and solvents were removed fromthe filtrate, followed by washing with n-hexane to additionally obtainyellow solid(320 mg, 0.70 mmol)(total 44% yield).

¹H NMR (500 MHz, CDCl₃): 0.96 (3H, s), 1.16 (3H, s), 1.91 (3H, s), 1.93(3H, s), 1.96 (3H, s), 1.97 (3H, s), 5.98 (1H, d), 7.07 (1H, t), 7.23(1H, d), 7.35 (1H, t), 7.49 (1H, d), 7.70 (1H, d).

The above synthesizeddimethylsilylene(tetramethylcyclopentadienyl)(indenyl)zirconiumdichloride (1.049 g, 2.3 mmol) was put in a mini bombe in a glove box.And, platinum oxide (52.4 mg, 0.231 mmol) was additionally put in themini bombe, the mini bombe was assembled, and then, anhydrous THF (30mL) was introduced into the mini bombe using a canuula, and hydrogen wasfilled to the pressure of about 30 bar. Subsequently, the mixturecontained in the mini bombe was stirred at about 60° C. for about oneday, and then, the mini bombe was cooled to room temperature, and whilegradually decreasing the pressure of the mini bombe, hydrogen wasreplaced with argon.

Meanwhile, celite dried in an oven of about 120° C. for about 2 hourswas laid in a schlenk filter, and using the same, the reaction productof the mini bombe was filtered under argon. By the celite, the PtO₂catalyst was removed from the reaction product. Subsequently, thecatalyst-removed reaction product was decompressed to remove solvents,thus obtaining a light yellow solid product (0.601 g, 1.31mmol, Mw:458.65 g/mol).

¹H NMR (500 MHz, CDCl₃): 0.82 (3H, s), 0.88 (3H, s), 1.92 (6H, s), 1.99(3H, s), 2.05 (3H, s), 2.34 (2H, m), 2.54 (2H, m), 2.68 (2H, m), 3.03(2H, m), 5.45 (1H, s), 6.67 (1H, s).

Synthesis Example 4 A First Metallocene Compound

4-1 Preparation of a Ligand Compound

In a dried 500 mL schlenk flask, tetramethylcyclopentadiene (TMCP, 3.6g, 30 mmol) was dissolved in THF (70 mL), and then, the solution wascooled to −78° C. Subsequently, n-BuLi (2.5M, 13 mL, 32 mmol) was slowlyadded dropwise to the solution, and then, the obtained solution wasstirred at room temperature overnight.

Meanwhile, in a separate 500 mL schlenk flask,dichloro(methyl)propylsilane was dissolved in n-hexane, and then, thesolution was cooled to −78° C. Subsequently, the TMCP-lithiationsolution prepared above was slowly added to the solution. And, theobtained solution was stirred at room temperature overnight to obtain anintermediate

¹H NMR (500 MHz, CDCl₃): 0.21 (3H, s), 0.94 (3H, t), 1.26-1.42 (4H, m),1.81 (6H, s), 1.98 (6H, s), 3.10 (1H, s).

In a dried 500 mL schlenk flask, indene (3.5 mL, 30 mmol) was dissolvedin THF (50 mL), and then, the solution was cooled to −78° C.Subsequently, n-BuLi (2.5M, 13 mL, 32 mmol) was slowly added dropwise tothe solution, and then, the obtained solution was stirred at roomtemperature for about 1.5 hours.

Meanwhile, in a separate 500 mL schlenk flask, the above synthesizedintermediate was dissolved in THF, and the solution was cooled to −78°C. Subsequently, the indene-lithiation solution prepared above wasslowly added to the solution. And, the obtained solution was stirred atroom temperature for about 2 hours to obtain a reddish purple solution.

Thereafter, water was poured into the reactor to finish thereaction(quenching), and an organic layer was extracted with ether fromthe mixture. And, the organic layer was decompressed to removed thesolvent, thus obtaining a product in the form of yellow oil (9.7 g, 30mmol, >99% yield).

¹H NMR (500 MHz, CDCl₃): −0.57 (1.5H, s), −0.29 (1.5H, s), −0.11 (3H,s), 0.72 (3H, t), 1.07-1.28 (4H, m), 1.59 (6H, d), 1.66 (6H, d),2.86-3.06 (1H, m), 3.22-3.25 (1H, m), 6.33 (1H, dd), 6.68 (1H, d),6.97-7.12 (2H, m), 7.20-7.36 (2H, m).

4-2 Preparation of a Metallocene Compound

Into a 250 mL schlenk flask,methylpropyl(indenyl)(tetramethylcyclopentadienyl)silane synthesizedabove (9.7 g, 30 mmol) was dissolved in THF (80 mL). And, the solutionas cooled to −78° C., n-BuLi (2.5M, 25 mL, 63 mmol) was slowly addeddropwise to the solution, and the obtained solution was stirred at roomtemperature overnight.

Meanwhile, in a separate 250 mL schlenk flask, ZrCl₄(THF)₂ (3.7 g, 9.7mmol) was dispersed in toluene(80 mL), and the obtained mixture wascooled to −78° C. Subsequently, the lithiated ligand solution preparedabove was slowly introduced into the mixture. And, the obtained mixturewas stirred overnight to obtain an orange suspension.

The suspension was decompressed to remove half of the solvent, and thesuspension was filtered to remove LiCl contained in the suspension.Thereafter, the solvent was removed from the filtered solution, and theobtained material was precipitated in toluene and pentane to obtain anorange solid product (8.7 g, 18 mmol, 60% yield).

¹H NMR (500 MHz, CDCl₃): 0.95 (3H, s), 1.15 (3H, s), 1.22 (2H, t), 1.17(3H, t), 1.90 (3H, s), 1.74-1.80 (2H, m), 1.92 (3H, s), 1.97 (6H, t),5.98 (1H, d), 7.07 (1H, t), 7.23 (1H, m), 7.35 (1H, t), 7.45-7.50 (1H,m), 7.70 (1H, d).

The above synthesizedmethylpropylsilylene(tetramethylcyclopentadienyl)(indenyl)zirconiumdichloride (4.837 g, 10 mmol) was put in a mini bombe in a glove box.And, platinum oxide (0.227 g, 1.0 mmol) was additionally put in the minibombe, the mini bombe was assembled, and then, anhydrous THF (50 mL) wasintroduced into the mini bombe using a canuula, and hydrogen was filledto the pressure of about 30 bar. Subsequently, the mixture contained inthe mini bombe was stirred at about 60° C. for about one day, and then,the mini bombe was cooled to room temperature, and while graduallydecreasing the pressure of the mini bombe, hydrogen was replaced withargon.

Meanwhile, celite dried in an oven of about 120° C. for about 2 hourswas laid in a schlenk filter, and using the same, the reaction productof the mini bombe was filtered under argon. By the celite, the PtO₂catalyst was removed from the reaction product. Subsequently, thecatalyst-removed reaction product was decompressed to remove solvents,thus obtaining off-white sticky solid product (2.8 g, 5.75 mmol, Mw:486.71 g/mol). The solid was dissolved in toluene and prepared as astock solution, and refrigerated.

¹H NMR (500 MHz, CDCl₃): 0.80 (3H, s), 0.86 (3H, s), 1.12 (2H, m), 1.32(2H, m), 1.41 (2H, s), 1.54 (2H, m), 1.65 (2H, m), 1.84 (2H, m), 1.91(6H, d), 1.93 (3H, s), 1.99 (3H, s), 2.25 (2H, m), 2.37 (2H, m), 2.54(2H, m), 2.99 (2H, m), 5.45 (1H, s), 6.67 (1H, s).

Synthesis Example 5 A Second Metallocene Compound

5-1 Preparation of a Ligand Compound

Into a dried 250 mL schlenk flask, 11.618 g (40 mmol) of4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene was introduced, and 100mL of THF was introduced under argon. A diethylether solution was cooledto 0° C., and then, 18.4 mL of nBuLi solution (2.5 M, 46 mmol, inhexane) was slowly added dropwise. The temperature of the reactionmixture was slowly raised to room temperature, and then, the mixture wasstirred until the next day. In a separate 250 mL schlenk flask, asolution of 12.0586 g(40 mmol, purity 90% calculated)dichloromethyltethersilane and 100 mL hexane was prepared, and theSchlenk flask was cooled to −30° C., and then, the lithiated solutionwas added dropwise thereto. After finishing the introduction, thetemperature of the mixture was slowly raised to room temperature, andthen, stirred for a day. Next day, NaCp (2M, in THF 33.6 mL) was slowlyadded and stirred for a day, and then, 50 mL of water was introduced inthe flask to quench, and an organic layer was separated and dried withMgSO₄. As the result, 23.511 g (52.9 mmol) of oil was obtained (NMRbased purity/wt %=92.97%. Mw=412.69).

5-2 Preparation of a Metallocene Compound

Into a 250 mL schlenk flask dried in an oven, the ligand was introducedand dissolved in 80 mL of toluene and 19 mL of MTBE (160 mmol, 4equiv.), and then, 2.1 equivalents of nBuLi solution(84 mmol, 33.6 mL)was added to lithiate until the next day. In a glove box, 1 equivalentof ZrCl₄(THF)₂ was put in a 250 mL schlenk flask, and ether wasintroduced to prepare a suspension. Both flasks were cooled to −20° C.,and then, ligand anion was slowly added to the Zr suspension. After theintroduction was finished, the temperature of the reaction mixture wasslowly raised to room temperature. After stirring for a day, MTBE in themixture was filtered with a Schlenk Filter under argon, and the producedLiCl was removed. The remaining filtrate was removed by vacuum suction,and pentane was added to a small amount of dichloromethane at the volumeof a reaction solvent. Wherein, the reason why pentane is added is thatsynthesized catalyst precursor has decreased solubility in pentane andpromotes crystallization. The slurry was filtered under argon, and thefilter cake remaining on the top and the filtrate were respectivelyanalyzed by NMR to confirm whether or not catalyst was synthesized, andweighed in a glove box and sampled to confirm yield and purity(Mw=715.04).

¹H NMR (500 MHz, CDCl₃): 0.60 (3H, s), 1.01 (2H, m), 1.16 (6H, s), 1.22(9H, s), 1.35 (4H, m), 1.58 (4H, m), 2.11 (1H, s), 3.29 (2H, m), 5.56(1H, s), 5.56 (2H, m), 5.66 (2H, m), 7.01 (2H, m), 7.40 (3H, m), 7.98(2H, m)

Synthesis Example 6 A Second Metallocene Compound

6-1 Preparation of a Ligand Compound

6-tert-butoxyhexyl chloride and sodium cyclopentadiene(2 equivalents)were introduced in THF and stirred. After the reaction was completed,the reaction mixture was worked-up with water and an excessive amount ofcylopentadiene was distilled and removed. To 4.45 g (20 mmol) of6-tert-butoxyhexylcyclopentadiene obtained by the above process, 27 mLof toluene was added. The temperature was lowered to −20° C., 8.8 mL ofn-BuLi solution (2.5 M, in hexane, 22 mmol) was added dropwise, and themixture was stirred at room temperature overnight.

Into a dried 250 mL Schlenk flask, 5.8 g (20 mmol) of4-(4-(tert-butyl)phenyl)-2-isopropyl-1H-indene was introduced, and 33 mLof MTBE was introduced. The temperature was lowered to −20° C., and 8.8mL of n-BuLi solution (2.5 M, in hexane, 22 mmol) was added dropwise,and the mixture was stirred at room temperature overnight. Thetemperature was lowered to −20° C., and 1.5 equivalents ofdichlorodimethyl silane was introduced. The reaction mixture was stirredovernight, and distilled to remove an excessive amount ofdichlorodimethyl silane.

The lithiated 6-tert-butoxyhexylcyclopentadiene solution was introducedinto the flask, and stirred overnight. By workup of the ligandsynthesized by the above process, a ligand compound was obtained.

6-2 Preparation of a Metallocene Compound

11.4 g (20 mmol) of the ligand compound synthesized in 6-1 was dissolvedin 50 mL of toluene, about 16.8 mL of n-BuLi solution(2.5 M, in hexane,42 mmol) was added dropwise, and the mixture was stirred overnight. 20mmol of ZrCl₄(THF)₂ was introduced and stirred overnight, and after thereaction was completed, the reaction mixture was filtered to removeLiCl. All the solvents were removed, followed by crystallization withhexane and purification to obtain different stereoisomers of ametallocene compound(A, B form) ata ratio of 1.3:1.

¹H NMR (500 MHz, C₆D₆):

Form A: 0.58 (3H,s), 0.55 (3H,s), 0.93-0.97(3H,m), 1.12 (9H,s), 1.28(9H,s), 1.27 (3H,d), 1.35-1.42 (1H,m), 1.45-1.62(4H,m), 2.58-2.65(1H,m), 2.67-2.85(2H,m), 3.20 (2H,t), 5.42 (1H,m), 5.57 (1H, m), 6.60(1H, m), 6.97 (1H, dd), 7.27 (1H, d), 7.39-7.45 (4H, m), 8.01 (2H, dd)

Form B: 0.60 (3H,s), 0.57 (3H,s), 0.93-0.97(3H,m), 1.11 (9H,s), 1.28(9H,s), 1.32 (3H,d), 1.35-1.42 (1H,m), 1.45-1.62(4H,m), 2.58-2.65(1H,m), 2.67-2.85(2H,m), 3.23 (2H,t), 5.24 (1H,m), 5.67 (1H, m), 6.49(1H, m), 6.97 (1H, dd), 7.32 (1H, d), 7.39-7.45 (4H, m), 8.01 (2H, dd)

Comparative Synthesis Example 1 A Second Metallocene Compound 1-1Preparation of a Ligand Compound

t-Butyl-O—(CH₂)₆—Cl was prepared using 6-chlorohexanol by a methoddescribed in the document(Tetrahedron Lett. 2951 (1988)), and reactedwith NaCp to obtain t-Butyl-O—(CH₂)₆—C₅H₅ (yield 60%, b.p. 80° C./0.1mmHg).

1-2 Preparation of a Metallocene Compound

And, t-Butyl-O—(CH₂)₆—C₅H₅ was dissolved in THF at −78° C., and n-BuLiwas slowly added thereto, and then, the temperature was raised to roomtemperature, and the mixture was reacted for 8 hours. The synthesizedlithium salt solution was slowly added to a suspension of ZrCl₄(THF)₂(1.70 g, 4.50 mmol)/THF(30 ml) at −78° C., and the solution was furtherreacted at room temperature for 6 hours.

All the volatiles were vacuum dried, and hexane was added to theobtained oily liquid to filter. The filtered solution was vacuum dried,and then, hexane was added to precipitate at low temperature(−20° C.).The obtained precipitate was filtered at room temperature to obtain acompound [tBu-O—(CH₂)₆—C₅H₄]₂ZrCl₂ in the form of white solid (yield92%).

¹H NMR (300 MHz, CDCl₃): 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6 Hz, 2H),3.31 (t, 6.6 Hz, 2H), 2.62 (t, J=8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H)

Comparative Synthesis Example 2 A Second Metallocene Compound

2-1 Preparation of a Ligand Compound

Into a dried 250 mL Schlenk flask, 3.7 g (40 mmol) of 1-chlorobutane wasintroduced, and dissolved in 40 mL of THF. 20 mL of sodiumcyclopentadienylide THF solution was slowly added thereto, and then, themixture was stirred overnight. To the reaction mixture, 50 mL of waterwas added to quench, it was extracted with ether(50 mL×3), and then, thecollected organic layer was sufficiently washed with brine. Remainingmoisture was dried with MgSO₄ and filtered, and then, the solvents wereremoved by vacuum suction, thus obtaining a dark brown viscose product2-butyl-cyclopenta-1,3-diene with quantitative yield.

2-2 Preparation of a Metallocene Compound

Into a dried 250 mL Schlenk flask, about 4.3 g(23 mmol) of the ligandcompound synthesized in 2-1 was introduced, and dissolved in about 60 mLof THF. About 11 mL of n-BuLi solution (2.0M, in hexane, 28 mmol) wasadded thereto, the mixture was stirred overnight, and then, the solutionwas slowly added to a flask containing 3.83 g(10.3 mmol) of ZrCl₄(THF)₂dispersed in about 50 mL of ether, at −78° C.

Upon raising the temperature of the reaction mixture to roomtemperature, light brown suspension turned into cloudy yellowsuspension. After stirring overnight, all the solvents were dried, about200 mL of hexane was added to sonicate and sink, and then, the hexanesolution floating on the upper layer was decanted with a cannula andcollected. This process was repeated twice to obtain a hexane solution,which was dried by vacuum suction, and it was confirmed that a compoundbis(3-butyl-2,4-dien-yl) zirconium(IV) chloride in the form of lightyellow solid was produced.

¹ H NMR (500 MHz, CDCl₃): 0.91 (6H, m), 1.33 (4H, m), 1.53 (4H, m), 2.63(4H, t), 6.01 (1H, s), 6.02 (1H, s), 6.10 (2H, s), 6.28 (2H, s)

Preparation Example of a Hybrid Supported Metallocene Catalyst>Preparation Example 1

Into a 20 L SUS high pressure reactor, 2.0 kg of toluene and 1000 g ofsilica (Grace Davison, SP2410) were introduced, and stirred whileraising the temperature of the reactor to 40° C. Into the reactor, 5.7kg of methylaluminoxane(10wt % in toluene, manufactured by AlbemarleCompany) was introduced, the temperature was raised to 70° C., and then,the mixture was stirred at about 200 rpm for about 12 hours. Thereafter,the temperature of the reactor was lowered to 40° C., and stirring wasstopped. And, the reaction product was left for about 10 minutes, andthen, decanted. Again, 2.0 kg of toluene was added to the reactionproduct, the mixture was stirred for about 10 minutes, stirring wasstopped, and the mixture was left for about 30 minutes, and then,decanted.

Into the reactor, 2.0 kg of toluene was introduced, and subsequently,the compound prepared in Synthesis Example 1(60 mmol), the compoundprepared in Synthesis Example 5(10 mmol) and 1000 mL of toluene wereintroduced. The temperature of the reactor was raised to 85° C., and thereaction mixture was stirred for about 90 minutes.

Thereafter, the reactor was cooled to a room temperature, stirring wasstopped, and the reaction product was left for about 30 minutes, andthen, decanted. Subsequently, 3 kg of hexane was introduced into thereactor, the hexane slurry solution was transferred to a 20L filterdryer and filtered, and vacuum dried at 50° C. for about 4 hours toobtain 1.5 kg of a supported catalyst.

Preparation Example 2

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 2(60 mmol) and Synthesis Example 5(10 mmol) were used.

Preparation Example 3

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 4(60 mmol) and Synthesis Example 6(10 mmol) were used.

Preparation Example 4

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 3(60 mmol) and Synthesis Example 6(10 mmol) were used.

Comparative Preparation Example 1

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 1(60 mmol) and Comparative Synthesis Example 1(10mmol) were used.

Comparative Preparation Example 2

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 2(60 mmol) and Comparative Synthesis Example 2(10mmol) were used.

Comparative Preparation Example 3

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 3(60 mmol) and Comparative Synthesis Example 2(10mmol) were used.

Comparative Preparation Example 4

A hybrid supported metallocene catalyst was prepared by the same methodas Preparation Example 1, except that the metallocene compounds ofSynthesis Example 4(60 mmol) and Comparative Synthesis Example 1(10mmol) were used.

TABLE 1 Comparative Comparative Comparative Comparative PreparationPreparation Preparation Preparation Preparation Preparation PreparationPreparation Example 1 Example 2 Example 3 Example 4 Example 1 Example 2Example 3 Example 4 Support form Hybrid Hybrid Hybrid Hybrid HybridHybrid Hybrid Hybrid Composition of Synthesis Synthesis SynthesisSynthesis Synthesis Synthesis Synthesis Synthesis metallocene Example 1/Example 2/ Example 4/ Example 3/ Example 1/ Example 2/ Example3/ Example4/ compound Synthesis Synthesis Synthesis Synthesis ComparativeComparative Comparative Comparative Example 5 Example 5 Example 6Example 6 Synthesis Synthesis Synthesis Synthesis Example 1 Example 2Example 2 Example 1 Rate of transition 6:1 6:1 6:1 6:1 6:1 6:1 6:1 6:1metal compound (mole ratio)

<Preparation Example of Polyolefin>

Ethylene-1-hexene copolymerization

As a polymerization reactor, a 140L continuous polymerization reactorcapable of progressing isobutene slurry loop process and driven at areaction flow rate of about 7 m/s was prepared. And, into the reactor,reactants required for olefin polymerization as described in Table 2were continuously introduced.

As a supported catalyst for each olefin polymerization reaction, thoseprepared in Preparation Examples as described in Table 1 were used, andthe supported catalyst was mixed with isobutene slurry and introduced.

The olefin polymerization reaction was conducted at a pressure of about40 bar and a temperature of about 84° C.

TABLE 2 Compar- Compar- Compar- Compar- ative ative ative ative Example1 Example2 Example 3 Example 4 Example 5 Example 6 Example 1 Example 2Example 3 Example 4 Catalyst Prepa- Prepa- Prepa- Prepa- Prepa- Prepa-Compar- Compar- Compar- Compar- ration ration ration ration rationration ative ative ative ative Example 1 Example 2 Example 1 Example 2Example 3 Example 4 Prepa- Prepa- Prepa- Prepa- ration ration rationration Example 1 Example 2 Example 3 Example 4 Ethylene 40 40 40 40 4040 40 40 40 40 input (kg/hr) Hydrogen 15 17 15 15 18 17 11.5 9 10 11input (ppm) Hexene 13 12.5 12 11 11 12 14 14.5 14 13 input (wt %) Slurry560 560 560 559 560 562 559 558 560 561 Density (g/L) Activity (kgPE/6.5 5.4 5.2 4.5 7.1 6.5 6.9 6.6 5.5 7.0 kgSiO2 · hr) Bulk density 0.400.42 0.42 0.42 0.42 0.42 0.40 0.41 0.41 0.40 (g/mL)

Experimental Example

For the polyolefins prepared in Examples and Comparative Examples, theproperties were measured as follows, and the results were respectivelyshown in the following Table 3 and Table 4.

In order to measure dart drop impact strength, the obtained polyolefinwas treated with an antioxidant (Irganox 1010+Igafos 168, CIBA Company),and then, granulated at an extrusion temperature of 180˜210° C. usingtwin screw extruder (W&P Twin Screw Extruder, 75 phi, L/D=36).

(1) Density: measured according to ASTM D1505 standard

(2) Melt Index (MI_(2.16)) : measured according to ASTM D1238 (conditionE, 190° C., 2.16 kg load) standard.

(3) MFRR(MI_(21.6)/M_(12.16)): a rate calculated by dividing M_(121.6)(ASTM D1238, 190° C., load of 21.6 kg) by MI_(2.16) (ASTM D1238, 190°C., load of 2.16 kg).

(4) Dart drop impact strength: Using a single screw extruder(YoojinEngineering, Single Screw Extruder, Blown Film M/C, 50 phi), inflationmolding was conducted at an extrusion temperature of 130˜170° C. to thethickness of 60 m. Wherein, die gap was set as 2.0 mm, and blown-upratio was set as 2.3. Each prepared film was measured 20 or more timesaccording to ASTM D1709 [Method A], and the average value was taken.

(5) Crystal Content According to Melting Temperature

Using Differential Scanning Calorimeter(device name: DSC8000,Manufacturing company: PerkinElmer), polyolefin was initially heated to160° C., and maintained for 30 minutes, thus removing heat historybefore measuring the sample.

The temperature was decreased from 160° C. to 122° C. and maintained for20 minutes, decreased to 30° C. and maintained for 1 minute, and then,increased again. Next, after heating to a temperature(117° C.) 5° C.lower than the initial heating temperature of 122° C., the temperaturewas maintained for 20 minutes, decreased to 30° C. and maintained for 1minute, and then, increased again. In this way, while graduallydecreasing the heating temperature at the same maintenance time andcooling temperature with (n+1)th heating temperature being 5° C. lowerthan nth heating temperature, the above process was repeated until thefinal heating temperature became 52° C. Wherein, the temperatureincrease and decrease speeds were respectively controlled to 20° C./min.Finally, while increasing the temperature from 30° C. to 160° C. at atemperature rise speed of 10° C./min, enthalpy change was observed tomeasure SSA thermogram.

From the SSA thermogram, using Tm and enthalpy(area S_(i)) of eachmelting peak, peak areas were quantified. Namely, the content ratio ofeach area was quantified as the rate of each area of S₁(40° C. or moreand less than 100° C.), S₂(100° C. or more and 120° C. or less),S₃(greater than 120° C.), to the areas(S₁+S₂+S₃) of melting peaks in theentire SSA thermogram.

(6) Weight average molecular weight(Mw) and molecular weightdistribution(MWD, polydispersity index), GPC curve: Using GPC (gelpermeation chromatography, manufactured by Waters corporation), theweight average molecular weight(Mw) and number average molecularweight(Mn) of polymer were measured, and molecular weightdistribution(PDI) was calculated by dividing the weight averagemolecular weight by the number average molecular weight.

Specifically, a sample was evaluated using Waters PL-GPC220, usingPolymer Laboratories PLgel MIX-B 300mm length column. The evaluationtemperature was 160° C., 1,2,4-trichlorobenzene was used as a solvent,and flow rate was 1 mL/min. A sample was prepared at a concentration of10 mg/10 mL, and then, fed in an amount of 200 μL. Using a calibrationcurve formed using a polystyrene standard, Mw AND Mn were measured. Asthe polystyrene standard, 9 kinds having molecular weight of2,000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000were used.

A graph showing the relationship between the density and dart dropimpact strength of polyolefin according to Examples and ComparativeExamples was shown in FIG. 2.

TABLE 3 Peak area Peak area Peak area content at Tm content at Tmcontent at Tm of 40~100° C. of 100~120° C. greater than 120° C.(S₁/(S₁ + (S2/(S₁ + (S₃/(S₁ + S₂ + S₃)) S₂ + S₃)) S₂ + S₃)) Example 10.34 0.56 0.10 Example 2 0.34 0.52 0.14 Example 3 0.35 0.53 0.12 Example4 0.35 0.54 0.11 Example 5 0.35 0.54 0.11 Example 6 0.34 0.52 0.14Comparative 0.35 0.59 0.06 Example 1 Comparative 0.34 0.59 0.07 Example2 Comparative 0.35 0.59 0.06 Example 3 Comparative 0.33 0.60 0.07Example 4

TABLE 4 Weight average Molecular Dart drop Density molecular weightweight MI_(2.16) impact (g/cm³) (g/mol) distribution (g/10 min) MFRRstrength (g) Example 1 0.918 114,000 2.5 0.96 23.6 1,390 Example 2 0.918111,000 2.5 1.09 23.5 1,250 Example 3 0.919 103,000 2.8 1.00 26.4 1,120Example 4 0.919 99,000 2.8 1.06 26.5 1,130 Example 5 0.920 104,000 2.81.00 25.5 1,020 Example 6 0.920 105,000 2.7 1.07 25.6 1,040 Comparative0.918 110,000 2.4 1.04 21.5 1,050 Example 1 Comparative 0.918 105,0002.5 1.13 22.2 1,010 Example 2 Comparative 0.919 100,000 2.5 1.20 23.8830 Example 3 Comparative 0.920 103,000 2.4 1.40 23.4 760 Example 4

Referring to Tables 3 and 4, it can be confirmed that polyolefin ofExamples 1 to 6 of the present invention exhibit dart drop impactstrength of 850 g or more, thus exhibiting excellent dart drop impactstrength, compared to Comparative Examples 1 to 4 having the samedensity.

1. A polyolefin having a density of 0.915 g/cm³ to 0.930 g/cm³ measuredaccording to ASTM D1505; and satisfying the following requirements 1) to3), when measuring a relative content of peak area according to meltingtemperature (Tm) using SSA (Successive Self-nucleation and Annealing)analysis: 1) a content(S₁) of peak area at Tm less than 100° C. is 0.33to 0.35; 2) a content(S₂) of peak area at Tm of 100° C. or more and 120°C. or less is 0.52 to 0.56; and 3) the a content(S₃) of peak area at Tmgreater than 120° C. is 0.10 to 0.14, provided that S₁+S₂+S₃=1.
 2. Thepolyolefin according to claim 1, wherein the SSA is conducted by heatingthe polyolefin to a first heating temperature of 120 to 124° C. usingdifferential scanning calorimetry, maintaining for 15 to 30 minutes, andthen, cooling to 28 to 32° C., and while decreasing heating temperatureby stages with (n+1)th heating temperature being 3 to 7° C. lower thannth heating temperature, repeating heating-annealing-quenching until afinal heating temperature becomes 50 to 54° C. , and finally, increasingthe temperature from 30° C. to 160° C. .
 3. The polyolefin according toclaim 1, which has a melt index (MI₂₁₆) measured under load of 2.16 kgat a temperature of 190° C. according to ASTM D1238 of 0.5 to 1.5 g/10min.
 4. The polyolefin according to claim 1, which has a haze measuredby a polyolefin film(BUR 2.3, film thickness 55 to 65 μm) prepared fromthe polyolefin using a film applicator, according to ISO 13468, of 12%or less.
 5. The polyolefin according to claim 1, which has a dart dropimpact strength measured by a polyolefin film(BUR 2.3, film thickness 55to 65 μm) prepared from the polyolefin using a film applicator,according to ASTM D 1709 [Method A], of 850 g or more.
 6. The polyolefinaccording to claim 1, wherein the polyolefin is copolymer of ethyleneand alpha olefin.
 7. The polyolefin according to claim 7, wherein thealpha olefin includes one or more selected from the group consisting ofpropylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene,1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-eicosene, norbornene, norbornadiene, ethylidene norbordene, phenylnorbordene, vinyl norbordene, dicyclopentadiene, 1,4-butadiene,1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methyl styrene,divinylbenzene, and 3-chloromethyl styrene.
 8. The polyolefin accordingto claim 1, wherein the polyolefin is prepared by polymerizing olefinmonomers, in the presence of a hybrid supported metallocene catalystcomprising one or more first metallocene compounds selected from acompound represented by the following Chemical Formula 1; one or moresecond metallocene compounds selected from a compounds represented bythe following Chemical Formula 2; and a carrier supporting the first andsecond metallocene compounds:

in the Chemical Formula 1, Q₁ and Q₂ are identical to or different fromeach other, and each independently, halogen, a C1-C20 alkyl group, aC2-C20 alkenyl group, a C2-C20 alkoxyalkyl group, a C6-C20 aryl group, aC7-C20 alkylaryl group, or a C7-C20 arylalkyl group; T₁ is carbon,silicon or germanium; M₁ is a Group 4 transition metal; X₁ and X₂ areidentical to or different from each other, and each independently,halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C6-C20 arylgroup, a nitro group, an amido group, a C1-C20 alkylsilyl group, aC1-C20 alkoxy group, or a C1-C20 sulfonate group; and R₁ to R₁₄ areidentical to or different from each other, and each independently,hydrogen, halogen, a C1-C20 alkyl group, a C1-C20 haloalkyl group, aC2-C20 alkenyl group, a C1-C20 alkyl silyl group, a C1-C20 silylalkylgroup, a C1-C20 alkoxysilyl group, a C1-C20 alkoxy group, a C6-C20 arylgroup, a C7-C20 alkylaryl group, or a C7-C20 arylalkyl group, or two ormore neighboring groups of R₁ to R₁₀ are connected with each other toform a substituted or unsubstituted aliphatic or aromatic ring;

in the Chemical Formula 2, Q₃ and Q₄ are identical to or different fromeach other, and each independently, halogen, a C1-C20 alkyl group, aC2-C20 alkenyl group, a C2-C20 alkoxyalkyl group, a C6-C20 aryl group, aC7-C20 alkylaryl group, or a C7-C20 arylakyl group; T₂ is carbon,silicon or germanium; M₂ is a Group 4 transition metal; X₃ and X₄ areidentical to or different from each other, and each independently,halogen, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C6-C20 arylgroup, a nitro group, an amido group, a C1-C20 alkylsilyl group, aC1-C20 alkoxy group, or a C1-C20 sulfonate group; and R₁₅ to R₂₈ areidentical to or different from each other, and each independently,hydrogen, halogen, a C1-C20 alkyl group, a C1-C20 haloalkyl group, aC2-C20 alkenyl group, a C2-C20 alkoxyalkyl group, a C1-C20 alkylsilylgroup, a C1-C20 silylalkyl group, a C1-C20 alkoxysilyl group, a C1-C20alkoxy group, a C6-C20 aryl group, a C7-C20 alkylaryl group, or a C7-C20arylalkyl group, provided that R₂₀ and R₂₄ are identical to or differentfrom each other, and each independently, a C1 to C20 alkyl group, or twoor more neighboring groups of R₁₅ to R₂₈ are connected with each otherto form a substituted or unsubstituted aliphatic or aromatic ring. 9.The polyolefin according to claim 8, wherein the compound represented bythe Chemical Formula 1 is one of compounds represented by the followingStructural Formulas:


10. The polyolefin according to claim 8, wherein the compoundrepresented by the Chemical Formula 2 is one of compounds represented bythe following Structural Formulas:


11. The polyolefin according to claim 8, wherein a mole ratio of thefirst and second metallocene compounds is 1.2:1 to 7.5:1.
 12. Thepolyolefin according to claim 8, wherein in the Chemical Formula 1, R₁₁to R₁₄ are each independently a C1 to C20 alkyl group, Ri is hydrogen ora C1 to C20 alkyl group, R₂ to R₁₀ are each hydrogen, Q₁ and Q₂ are eachindependently a C1 to C20 alkyl group or a C6 to C20 aryl group, X₁ andX₂ are each independently halogen, and M₁ is Ti, Zr or Hf.
 13. Thepolyolefin according to claim 8, wherein in the Chemical Formula 2, R₂₅and R₂₈ are each independently hydrogen, a C1 to C20 alkyl group, or aC2 to C20 alkoxyalkyl group, Q₃ and Q₄ are independently a C1 to C20alkyl group or a C2 to C20 alkoxyalkyl group, X₃ and X₄ are eachindependently halogen, and M₂ is Ti, Zr or Hf.